Efficient route for the construction of polycyclic systems from bioderived HMF

The first synthesis of tricyclic compounds from biobased
5-hydroxymethylfurfural (HMF) is described. The Diels-Alder reaction was used
to implement the transition from HMF to non-planar framework, which possessed
the structural cores of naturally occurring biologically active compounds and
building blocks of advanced materials. A one-pot, three-step sustainable
synthesis in water was developed starting directly from HMF.

The reduction of
HMF led to 2,5-bis(hydroxymethyl)furan (BHMF), which could be readily involved
in the Diels-Alder cycloaddition reaction with HMF-derived maleimide, followed
by hydrogenation of the double bond. The described transformation was
diastereoselective and proceeded with a good overall yield. The applicability
of the chosen approach for the synthesis of analogous structures containing
amine functionality on the side chain was demonstrated. To produce the target
compounds, only platform chemicals were used with carbohydrate biomass as the
single carbon source.